FREE ENERGY

Free energy may refer to: Free energy is the energy in a physical system that can be converted to do work, in particular:
Helmholtz free energy, the energy that can be converted into work at a constant temperature and volume Gibbs free energy, the energy that can be converted into work at a constant temperature and pressure

Helmholtz & Gibbs introduced 2 independent free energy functions

Helmholtz free energy A
A =E TS
(eq. 1)

Gibbs free energy G G = H - TS (eq.2)

 Process is reversible E = qrev - wmax Constant temperature E = TS - wmax

(eq. 3)

(eq. 4)

Combining Equation (1) with Equation (4) yields: wmax = A (eq. 5)

 Constant pressure H = E + PV (eq. 6)

Substituting Equation (6) and Equation (1) into Equation (2) gives: G = A + PV (eq. 7)

 Substituting Equation (5) into Equation (7) yields: G = wmax PV Irreversible spontaneous process, TdS > dqirrev combined with dE = dq dw yields:

(eq. 8)

TdS > dE + PdV

(eq. 9)

Substituting Equation (8) into Equation (9) along with the first law (dE = dq dw) and the second law (dq = TdS) gives:

dG < VdP SdT

(eq. 10)

At constant temperature and pressure (dT = 0 and dP = 0), Equation (10) becomes:

(dG)T.P < 0

(eq. 11)

 If G ve ~ total entropy in the system and surroundings is increased ~ reaction may proceed If G +ve, ~ total entropy in the system and surroundings is decreased ~ reaction will not proceed

Relationship between H, S and G

H
Negative Negative Positive Positive

S
Positive Negative Positive Negative

G
Negative at all temperatures Negative at low temperatures Negative at high temperatures Positive at all temperatures

FREE ENERGY OF FORMATION AND STANDARD FREE

The free energy of any element in its standard state (1 atmospheric pressure and 25C) is zero. The standard free energy of formation of a compound is:

Gfo = Hfo - T Sfo

where: The superscript denotes the standard state Gf denotes Gibbs free energy of formation Hf denotes standard heat of formation Sf denotes entropies for the formation

The free energy change of a reaction can be calculated by :

 EXAMPLE 1: Calculate the free energy of formation of L-alanine at 25oC for the reaction :
3C(graphite) + 7/2 H2(g) + O2(g) + N2(g) C3H7O2N(s)

(SOala=30.88; SoC=1.36; SoH2=31.21; SoO2=49.00; SoN2=45.77)

 ANSWER: Hof[C3H7O2N(s)]=-134.50 kcal

So298 = Soproducts -So reactants

= [30.88][3(1.36)+7/2 (31.21)+49.00+ (45.77)]
= -154.33 cal/mol K

Gof = Hof - T Sof

= -134500 298(-154.33)
= -88.51 kcal/mol

EXAMPLE 2:
We can know whether chemical or biological reactions are spontaneous and calculate the change in free energy for the reaction. Let us examine the synthesis of glucose:

6CO2(g) + 6H2O(l)

C6H12O6(s) + 6O2(g)

(GoC6H12O6=-217.63;GoO2=0;GoCO2=-94.26;GoH2O=-54.64)

The change in free energy for the reaction is given by:

Go= [-217.63+0]-[6(-94.26)+6(-54.64)] = 675.77 kcal The above synthetic reaction does not occur spontaneously due to the positive sign in the change in free energy for the reaction.

THANK YOU
N

WASSALAM
By :::

~Nurish Ezzantie Bt Mishan ~Nur Atiqah Bt Anwa ~Nur Aisyah Bt Ahmad Noruddin@Nordin